Trifluoromethyl-nitro-phenyl-thio(dithio)phosphates

ABSTRACT

Trifluoromethyl-nitro-phenyl-thio(dithio)phosphates of the formula   WHEREIN R1 represents methyl or ethyl, R2 represents alkyl with 1 to 5 carbon atoms, and X represents oxygen or sulphur, processes for their manufacture, and their use in pest control.

United States Patent Kristiansen Feb. 18,1975

TRIFLUOROMETHYL-NITRO-PHENYL- THIO(DITHIO )PHOSPHATES 3/1963 Miihlmann et a1 260/954 X 3,636,143 l/1972 Schrader et a1 260/954 Primary Examiner'Ant0n H. Sutto Attorney, Agent, or Firm-Frederick l-l. Rabin [57] ABSTRACT Trifluoromethyl-nitro-phenyl-thio(dithio)phosphates of the formula OF OR NO S wherein R represents methyl or ethyl, 1 R represents alkyl with l to 5 carbon atoms, and X represents oxygen or sulphur, processes for their manufacture, and their use in pest control.

7 Claims, N0 Drawings TRIFLUOROMETHYL-NlTRO-PHENY L-THIO( DI- THIO )PHOSPHATES The present invention relates to trifluoromethylnitrophenyl-thio(dithio)phosphates, processes for their manufacture, and to their use in pest control.

The thiolphosphoric acid esters have the formula X OR The alkyl groups with 1 to carbon atoms represented by R canbe straightchain or branched. Examples of such groups include: propyl, isopropyl, n-, i-, sec. and tert. butyl, n-pentyl, i-pentyl.

The compounds of the formula I can be manufactured by the following known methods: V

R X u 3 .1 Q acid acceptor; I

(III) CF I In the formulae II and IV, R, and R have the same meaning as given for the formula I and Me represents an alkali metal, in particular sodium or potassium, or an ammonium group, e.g. the group (R N H, wherein R represents hydrogen or alkyl, in particular alkyl with 1 to 4 carbon atoms.

Suitable acid acceptors are: tertiary amines, e.g. trialkylam'ines, pyridine, dialkyl anil'ines; inorganicv bases, e.g. hydrides, hydroxides; carbonates and bicarbonates of alkali metals and alkaline earth metals. It issometimes necessary to use catalysts in the reactions, e.g.

copper or copper chloride. The processes arecarried dialkylated carboxylic acid amides; aliphatic, and halogenated hydrocarbons, in particular benzene, toluene,

v formylcarbamoylmethyl)-dithiophosphate O,O-dimethyl-O-p-nitrophenylthiophosphate xylene, chloroform, chlorobenzene, nitriles, e.g. acetonitrile; dimethyl sulphoxide; ketones, e.g. acetone, methyl ethyl ketone; water.

The starting'materials of the formulae II, III, and IV are known, and can be manufactured in analogous manner to the methods described in e.g. Organic Reactions II and Journal Org.Chem. 27 4661 (1962) or Journal Am. Chem.Soc74 3011(1952).

The compounds of the formula I have a broad biocidal activity spectrum and can therefore be used for combating various plant and animal pests. In particular they are suitable for combating insects of the families:

Acrididae, Blattidae, Gryllidae, Gryllotalpida e, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, pseudococcidae', Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae,

The following active substances are examples of suitable additives:

ORGANIC PHOSPHORUS COMPOUNDS Bis-0,0-diethylphosphoric acid anhydride (TEPP) Dimethyl-(2,2,2-trichloro-l-hydroxyethyl)- phosphonate (TRICHLORFON)v I 1,Z-dibromo-2,2-dichloroethyldimethylphosphate (NALED) 2,2 dichlorovinyldimethylphosphate (DI- Cl-ILORVOS) Z-methoxycarbamyll -methylvinyldimethylphosphate (MEVINPHOS) Dimethyl-l-methyl-2-(methylcarbamoyl)-' vinylphosphate cis (MONOCROTOPHOS) 3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DICROTOPHOS) I 2-chloro-2- diethylcarbamoyl-l-methylvinyldimethylphosphate (PHOSPHAMIDON) 0,0-diethyl-O(or S')-2-(ethylthio)-ethylthiophosphate (DEMETON) S-ethylthioethyl-QO-dimethyl-dithiophosphate (THI- OM-ETON) 0,0-di'ethyl-S-ethylmercaptomethyldithiophosphate (PI-IORATE) 0,0-diethyl-S-2-(ethylthio)ethyldithiophosphate- (DI- SULFOTON) 2-(e'thylsulphinyl)ethylthiophosphate TON METHYL) 0,0-dimethyl-S-( l ,Z-dicarbethoxyethyldithiophosphate (MALATHION) 0,0,0,0-tetraethyl-S,S-methylene-bisdithiophosphate (ETHION) O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N- (OXYDEME- (FOR- MOTHION) 0,0-dimethyl-s-(N-methylcarbamoylrnethyl)- dithiophosphate (DIMETHOATE) (PA- 'RATHION-METHYL) O',O-diethyl-O-p-nitrophenylthiophosphate TII O (PARA- 9 l,2,3,4,l0,10-hexachloro-S ,7-epoxyl ,4,4a,5,6,7,8,8aoctahydro-endo-endo-S ,S-dimethanonaphthalene [ENDRIN] In addition to the properties cited hereinabove, the compounds of the formula I also display activity against representitives of the division Thallophyta. Thus a number of these compounds display bactericidal action. But they are active above all against phytopathogenic fungi which belong to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes. The compounds of the fomula I also evidence a fungitoxic action against fungi which attack the plants from the soil. Further, the new active substances are also suitable for freating seeds, fruit, tubers etc. to protect them'from fungus infections. The

compounds of the formula I are also suitable for combating plant pathogenic nematodes.

The compounds of the formula I may be used as pure active substance or together yvith suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions, in the conventional formulation which is commonly employed in application technology. Mentionmay also be made of cattle dips and spray races, in which aqueous.

preparations are used.

The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take, and be used in, the following forms: Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

Wettable powders, pasts, emulsions;

b. solutions.

To manufacture solid form's (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, S10 granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances ofthe formula I with polymer- 10 isable compounds I (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the.

a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/liter to 600 g/liter can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants. v

' It is also possible to obtain granules by compacting,

the carrier with the active substance and carriers and subsequently comminuting the product.

To these'mixtures can also be added additives which stabilise the activesubstance and/or non-ionic, anionic and cationic surface active substances, which, for example, improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycolethers ofmonoalkyl and dialkyl phenols having 5.to l5 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal alkaline earth metal-salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethyleneglycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Suitable carriers are, for

example, those mentioned for the solidforms of application. In some cases it is advantageous to use mixtures of different carriers. A's dispersing agents there can be used, for example, condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulphonic acids with phenoland formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulphonic acid, in addition, alkylaryl sulphonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleoyl et hionate, the sodium salts of oleoyl methyl tau- 1 1 ride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with the additives cited hereinabove, in such a manner that, the size of the solid particles does not exceed 0.02 to 0.04p. in wettable powders, and 0.03;]. in pastes. To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above, organic solvents, and water are used. Examples of suitable solvents are: alcohols, benzene, xylene, toluene, dimethyl sulphoxide, and mineral oil fractions which boil between 120 and 350C. The solvents must be practically odourless, not phytotoxic, and inert to the active substances. 7 Furthermore, the agents according to the invention can be applied to the form of solutions. Forthis purpose the active substances, or several active substances of the general formula 1, are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes and mineral oils, singly or in admixture with each other, can be used as organic solvents.

The content of active substance in the above described agents is between 0..l to 95 percent, in which connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5 percent or even pure active substance.

The active substances of the formula 1 can, for example, be formulated as follows:

Dusts The following-substances are used to manufacture (a) and percent and (b) a 2 percent dust:

a. 5 parts of active substance 95 parts of talcum b. 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum. The active substances are mixed with the carriers and ground. I

Granules The following substances are used to produce 5 percent granules:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts-of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on kaolin, and the acetone subsequently evaporated in vacuo.

Wettable Powder The following constituents are used for the preparation of (a) a 40 percent, (b) and (c) a 25 percent, and (d) a 10 percent wettable powder:

a. 40 parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silicic acid.

b. 25 parts of active substance,

4.5 parts of calcium lignin sulphonate,

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

c. 25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose Emulsifiable Concentrates The following substances are used to produce (a) a 10 percent and (b) a 25 percent emulsifiable concentrate:

a. 10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

b. 25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulphonate/fatty alcoholpoly- A glycol'ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene. From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.

Spray The following constituents are used to prepare a 5 percent spray:

, 5 parts of active substance, 1 part of epichlorohydrin, 94 parts of benzine (boiling limits l60l90C).

EXAMPLE 1 O-ethyl-S-n-propyl-O-( 3-trifluoromethyl-4- nitrophenyl )-thi olphosphate To -a solution of 20.7 g of 3-trifluoromethyl-4- nitrophenyl in ml of diethyl ether are added 10.12 ml of triethylamine. While stirring constantly, 20.3 g of O-ethyl-S-n-propyl-thiolphosphoric chloride are added dropwise at l0l5C. Stirring is then continued for 12 hours at room temperature. The mixture is washed with water, 3 percent Na CO solution, and again with water, and dried over anhydrous sodium sulphate.

The solvent is distilled off to give the compound of the formula with a refractive index of n,,20=l.4987.

The following compounds are also manufactured in analogous manner:

NO (EH 8 (nNSH S EXAMPLE 2 Insecticidal ingest poison action plants with Colorado potato bettle larvae (Lqminotarsa decemlineata The test was carried out at 24C and 60 percent relative hymidity. In the above test, the compounds according to Example 1 displayed good ingest poison action against Spadaptera littoralis, Heliol/zis and Lepu'notarsa decemlineata.

EXAMPLE 3 Action against child suppressalis Six rice plants at a time of the variety Caloro were transplanted into plastic pots (diameter at the top=l7cm) and reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L z3-4mm long) took place 2 days after the active substance had been applied in granule form 'to the paddy water (rate of application: 8 kg of active substance per hectare). Evaluation of the insecticidal action took place lO'days after application of the granules. v

The compounds according to Example I were active in the above test against Chilo suppressalis.

EXAMPLE 4 Sterilised compost earth was homogeneously mixed with a wettable powder containing 25 percent of active substance so that there resulted a rate of application of 8 kg of active substance per hectare.

Young zucchetti plants (Cucumis pepo) were put into plastic pots with the treated soil (3 plants per pot; diameter of pot-7 cm). Each pot was infected immediately afterwards with 5 Aulucophora femoralis and Pachmoda or Clzortop/tila larvae. The control was carried out 4, 8, l6 and 32 days after depositing the larvae.

At 80-100 percent kill after the f rst control, a fresh infestation with 5 larvae each was carried out in the same soil sample with 3 new zucchetti plants. If the activity was less than 80 percent, the remaining larvae remained in the soil sample until the control immediately following. If an active substance at a rate of application of 8 kg/ha still effected a percent kill, a further control with 4 and 2 kg of active substance per hectare was carried out.

In the above test, the compounds according to Example I displayed action against Aulacophora femoralis, Pachmoda and Chortophila larvae.

EXAMPLE 5 Action against ticks A. Rhipicephalus'bursa Five adult ticks or 50 tick larvae were counted into a glass tube and immersed for l to 2 minutes in2 ml-of an aqueous emulsion from an emulsion series each containing 100, I0, I and 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and placed on its head, so that the active substance emulsion could be adsorbed by the cotton wool. In the case of the adults evaluation took place after 2 weeks, and in that of the larvae after 2 days. Each test was repeated twice.

B. Boophilus microplus (larvae) Tests were carried out in each case with 20 OP- sensitive larvae using an analogous dilution series as in the case of test A. (The resistence refers to the tolerability of Diazinon). The compounds according to Example I acted in the above test against adults and larvae of Rhipicephalus bursa and sensitive and OP- resistent larvae of Boophilus microplus.

EXAMPLE 6 Acaricidal action Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the acaricidal action. The mobile stages which have migrated were sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth did not run off. The number of living and dead larvae, adults and eggs were evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the interim, the treated plants were kept in greenhouse compartments at 25C.

The compounds according to Example 1 were active in the above test against eggs, larvae and adults of Tetranychus urticae.

EXAMPLE 7 Action against soil nematodes To test the action against soil nematodes, the active substance (in the concentration indicated in each case) was applied to, and intimately mixed with, soil infected with root gall nematodes (M eloidgyne avenaria).

' Immediately afterwards, tomato cuttings were planted in the thus prepared soil in a series of tests and after a waiting time of 8 days tomatoes were sown in an thee stsedes V. 1 s In order to assess the nematocidal action, the galls present on the roots were counted 28 days after plant-.

ing and sowing respectively. The compounds according to Example 1 displayed good action against Meloidgyne avenaria.

EXAMPLE Herbicidal action on preemergence application a. The active substance, of a the form of 10 percent powder concentrate, was worked into garden soil in a concentration of 3 g of active substance per square metre. The following test plants were sown in the prepared soil:

Solanum Lycopersianum Setaria ilalica Avena sativa Lolium perenne Sinapis alba Vicia saliva The seed dishes were then kept in daylight in a greenhouse at 2225C and 50 to 70 percent relative humidity. The tests were evaluated after days.

'Composition of the powder concentrate 10 parts of active substance, 0.6 part of sodium dibutylnaphthalenesulphonate. '1 part of naphthalenesulphonic acid/phenolsulphonic acid/formaldehyde condensate (3:2:1), 10 parts of sodium aluminium silicate, 78.4 parts of kaolin.

b. Immediately after the test plants had been sown the active substances were applied in the form of an aqueous suspension (obtained from a 25 percent wettable powder) tothe surface of the soil. The seed dishes were then kept at 2223C and 50-70 percent relative humidity. The tests were evaluated after 28 days.

There were used as test plants:

Weeds:

A lopecurus m yosuroides lpomea pu rpurea Lolium multiflorum Poa trivialis Setaria italica Sinapis aIba Echinochloa crus galli 16' Digitaria sanguinalis Cultivated plants:

sugar beet In the above tests the compounds according to Example 1 displayed herbicidal action.

What is' claimed is: l. A compound of the formula X C15 R O wherein R represents methyl or ethyl; R represents propyl, isopropyl, n-butyl, isobutyl, sec.butyl, tert.bu tyl, n-pentyl or isopentyl; and X represents oxygen or sulphur.

2. The compound according to claim l, of the formula 3. The compound according to claim 1, of the formula 3 /OC H 0 N OP 5. The compound according to claim.l, of the formula v B ll 6. The compound according to claim 1, of the for mula I 0 CF 2 5 n 3 7. The compound according to claim 1, of the formula 

1. A COMPOUND OF THE FORMULA
 2. The compound according to claim 1, of the formula
 3. The compound according to claim 1, of the formula
 4. The compound of the formula
 5. The compound according to claim 1, of the formula
 6. The compound according to claim 1, of the formula
 7. The compound according to claim 1, of the formula 